Aqueous resin dispersion for floors, and floor polish using same

ABSTRACT

To provide a floor polish composition which has excellent gloss, black heel mark (BHM) resistance, scuff resistance, and storage stability, which in particular has removability, adhesive properties, stain resistance, and water resistance, which uses no aromatic vinyl monomers in an aqueous resin dispersion for floors and thus has no effects such as sick house syndrome, and which also uses no metal crosslinking and is thus excellent in environmental safety. An aqueous resin dispersion for floors in which a copolymer comprising the monomer units (a), (b), and (c) as the structural units is dispersed in water, wherein the content ratios of each monomer in said aqueous resin dispersion for floors, based on the total amount of all the monomers, are: (a) 1 to 70 wt. % vinyl monomer units with an alicyclic structure; (b) 5 to 50 wt. % vinyl monomer units with carboxyl groups; and (c) 5 to 90 wt. % non-aromatic vinyl monomer units other than (a) and (b) above; as well as a floor polish comprising the dispersion.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an aqueous resin dispersion for floorsand a floor polish composition using same.

2. Description of the Related Art

Floor polish compositions have been used on floor surfaces of wood floormaterials, chemical floor materials composed of synthetic resins,concrete or stone such as marble or the like to preserve the beauty ofthe floor material and to protect the floor surface. Floor polishcompositions are generally of oily type using solvents and of aqueous oremulsified composition type.

The classification of floor polish compositions is provided in thesection Definition of Terms in Testing Methods for Floor Polishes,General Rules, in “JFPA (Japan Floor Polish Association) Standard—00”.

Among the floor polishes mentioned in the standard, aqueous polymer-typecompositions have been most widely used as polishing agents for floors.Specific examples of aqueous polymer type floor polishes have beendisclosed in Japanese Patent Publications Nos. S44-24407 and S49-1458,Cosmetic Chemical Specialties, 61(9), 86 (1985), etc., and thosepolishes comprised acrylic copolymer emulsions, polyethylene waxemulsions, alkali solubilizable resins, plasticizers, and othercomponents.

Japanese Patent Publications Nos. S47-14019 and S47-15597 disclosedfloor polish compositions using polyvalent metal compounds and suitablefor wood floor materials, chemical floor materials composed of syntheticresins, and floor surfaces from concrete or stone such as marble or thelike. The polyvalent metal compounds in this case included heavy metalssuch as zinc, cobalt, cadmium, nickel, chromium, zirconium, tin,tungsten, aluminum, and the like, and floor polish compositions in whichthe metals formed complexes with amines or ammonia have been disclosed.

Floor polish composition using no such complexes have also beensuggested. For example, Japanese Patent Publication No. S60-48542suggested a method for dispersing zinc oxide in a copolymer emulsion,instead of using metal complexes. This method comprises a step ofdispersing zinc oxide, for example, by stirring and mixing, in anemulsion containing an acrylic copolymer, thereby making it possible toobtain a floor polish composition with good stability and releasing noamine odor during drying.

The above-mentioned polyvalent metal compounds have been added toimprove endurance, water resistance, and removability of floor polishcompositions. However, as concerns about environmental pollution havebeen growing in recent years, a demand was created for floor polishcompositions which are not directly related to environmental problemssuch as water contamination if handled under appropriate control, suchcompositions containing no polyvalent metal compounds (heavy metals andthe like) to prevent any possibility of such compositions becoming thenegative factors in terms of environmental pollution and safety.

Furthermore, because there is a risk that using zinc oxide will alsocause environmental pollution with a heavy metal, an attempt was made touse calcium as a metal crosslinking agent. For example, Japanese PatentApplication Laid-open No. H8-92529 disclosed a floor polish compositionusing calcium as a metal crosslinking agent. However, in compositions inwhich a crosslinking agent was simply replaced with calcium, a filmcould not be provided with sufficient endurance and wear resistancecomparable with those of the films obtained by metal crosslinkingemploying zinc that has usually been used, and in accordance with theabove-mentioned inventions, the insufficiency in endurance and wearresistance was compensated by causing a crosslinking reaction of anaqueous polyurethane resin and a calcium compound.

Furthermore, aqueous coating compositions containing no metalcrosslinking agents at all have also been suggested. For example, inaccordance with Japanese Patent Application Laid-open No. 2001-2980,endurance was increased by adding 0.1-100 wt. % amine compound to 100wt. % (solids) aqueous dispersion of a copolymer with a glass transitiontemperature of no more than 80° C. However, with this method, when thepolish was overcoated, amines penetrated into the film of prime polishlayer, thereby making it impossible to obtain sufficient gloss. Anotherdrawback was that the viscosity was increased degrading the coatingprocessability.

Japanese Patent Application Laid-open No. 2000-290596 disclosed apolishing agent composition for floors using a vinyl monomer with analicyclic structure. However, the specifically disclosed polymercontained a large amount of styrene and the disclosed compositionsrequired metal crosslinking. The problem associated with a floor polishcomposition produced by conducting metal crosslinking of such a polymercontaining a large amount of styrene was that the film obtained couldnot be removed to a sufficient degree with a neutral stripping agent andhad a limited usage.

It has been widely believed that among all the alicyclic vinyl monomerunits that have been used in the conventional aqueous resin dispersionsfor floors, styrene was a monomer unit indispensable for providing thecoated film with gloss. In recent years, the issues of sick house andsick school syndromes caused by construction materials have been raisedand a research has been started of the effect produced by unreactedstyrene monomer contained in a very small amount in styrene copolymersused in the floor polish compositions, in comparison with the indicatorsprovided by the government, and whether this effect can pose a problem.

On the other hand, there have been many reports that the air inside therooms in contemporary buildings was polluted with chemical substancesdue to a high degree of air tightness or because construction ortrimming materials releasing chemical substances were used, inparticular, in new or renovated buildings, this pollution causing avariety of physical disorders in the inhabitants.

The symptoms (called “sick house symptoms”) vary among the patients,many aspects of the disorders, beginning with patterns of symptomappearance, are not clear and a variety of complex factors have beenalso considered.

Typical examples of the factors causing the sick house symptoms includerelease of chemical substances from construction materials such asfinishing materials, including vinyl chloride wallpaper and the like,plywood for ceilings and floors, thermally insulating materials, paints,and the like, articles for daily use such as furniture, carpets,curtains, and the like, combustion gases from kitchen equipment, heatingequipment, and the like, building design and construction methods suchas methods protecting structures from ants and the like.

The main symptoms include skin irritation, eye pain, sore throat,headache, dizziness, and nausea. Some patients have breathingdifficulty.

Further, if a person became hypersensitive after initial exposure to acertain dose of chemical substances or after long-term exposure tolow-concentration chemical substances, he or she can thereafterdemonstrate hypersensitivity (“chemical substance hypersensitivity”)even with respect to extremely small amounts of chemical substances ofthe same system.

From among the chemical substances demonstrating a high degree ofpollution in indoor air, the Ministry of Health, Labor, and Welfare ofJapan on Dec. 22, 2000, has selected the following eight chemicalsubstances: “formaldehyde, toluene, xylene, paradichlorobenzene,ethylbenzene, styrene, chloropyriphos, and di-n-butyl phthalate”, onJul. 25, 2001, added the following three substances: “tetradecane,di-2-ethylhexyl phthalate, and diazinone” and presented guideline valuesfor indoor concentration of each of those substances. The guidelinevalues have been set in accordance with the decision based on thepresently available scientific information that no detrimental effectwill be produced on the health even if a person is exposed throughouthis/her life to those chemical substances at a concentration thereof ofno higher than the guideline value (however, formaldehyde has beenindicated to be toxic even in a short-period exposure).

As for the object of providing those guideline values, it was expectedthat they will make a contribution to the improvement of independentresidential housing structures, designs, and specifications, forexample, by preventing those involved in the residential housingconstruction industry from using substances for which the guidelinevalues may be exceeded in the products such as building materials,thereby enhancing the reduction of indoor concentration of volatileorganic compounds (VOC, organic compounds that are evaporated at normaltemperature; most of them have a boiling point of 25-50° C.) andensuring safe and pleasant residential environment.

Against this background, a demand arose for floor polish compositionswith a small content ratio of styrene as a monomer unit and floor polishcompositions containing substantially no styrene, those compositionsretaining the gloss of the conventional coating films.

On the other hand, monolayer flooring using solid sheets, compositeflooring with plywood, aggregated materials, or single-sheet laminatesas a base sheet covered on the surface thereof with decorative layers ofnatural wood or decorative paper obtained by special processing(printing), soundproofing flooring (wood flooring; a general termrelating to sheets subjected to processing for application to floors,including the above-described flooring) have been actively introduced inrecent years in general residential housing industry with the object ofreducing house dust and the like.

A problem associated with the maintenance of such flooring was that thefloor full-maintenance methods such as used for businesses have notspread into the field of residential housing and, actually, themaintenance methods designed for businesses cannot be easily introducedin residential housing. As a result, sufficient and appropriatemaintenance and control cannot be performed. In particular, the flooring(wood flooring) in general residential housing is often used in placeswhere water is used, for example, in the kitchens, dining rooms, livingrooms, washing spaces, dressing rooms, and the like, and floor polishcompositions for homes are required to have a high resistance to waterand stains.

Maintenance troubles associated with flooring are due to the fact thatresin-based floor polishes are coated repeatedly over a long time.Therefore, a coating film of an unnecessary large thickness is formedwhich can reduce the film strength or render a state in which strippingis difficult.

Furthermore, there are cases in which warping or tearing of flooringresults from using a large quantify of detergents and water, and casesin which improper adhesion and powdering of floor polishes and slipperystate of floors is caused by the problems associated with theapplication method.

The merits of wood floors are the beauty of wood texture, its softnessto touch, small weight and high processability. On the other hand,because wood is a porous material, it is sensitive to moisture and humidair, and deforms, cracks, warps, and shrinks because it can expand onadsorbing water and shrink on drying.

Thus, because wood is greatly affected by water, the amount of waterused during maintenance should be minimized and quick operations takinglittle time have to be conducted.

Furthermore, acidic or alkaline detergents not only cause swelling andshrinking of wood but also induce discoloration when penetrate deeplythereinto. As a result, the beauty inherent to wood is lost. Required inthe field of flooring maintenance are the maintenance control methodsproviding for appropriate removal of stains and a high level of safety,sanitary, and cleanliness, and producing no adverse effect on theflooring (wood flooring) beauty, and floor polish compositions suitablefor such methods.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an aqueous resindispersion for floors which demonstrates sufficient utility in floorpolish compositions containing substantially no styrene as a monomerunit and using no metal crosslinking. Another object of the presentinvention is to provide a floor polish composition which has excellentgloss, black heel mark (BHM) resistance, scuff resistance, and storagestability and in particular has removability, adhesive properties, stainresistance, and water resistance.

The results of the comprehensive study conducted by the inventors havedemonstrated that the above-described objects can be attained by using aspecific combination of monomers. This finding led to the creation ofthe present invention.

Thus, the present invention, in accordance with the first aspectthereof, provides an aqueous resin dispersion for floors in which acopolymer comprising the monomer units (a), (b), and (c) as thestructural units is dispersed in water, wherein the content ratios ofeach monomer in the aqueous resin dispersion for floors, based on thetotal amount of all the monomers, are:

-   -   1 to 70 wt. % vinyl monomer units with an alicyclic structure;    -   5 to 50 wt. % vinyl monomer units with carboxyl groups; and    -   5 to 90 wt. % non-aromatic vinyl monomer units other than (a)        and (b) above. In accordance with the second aspect of the        present invention, there is provided the above-described aqueous        resin dispersion for floors wherein the monomer unit (a)        comprises at least one compound selected from cyclohexyl        methacrylate and cyclohexyl acrylate.

From a different standpoint, in accordance with the third aspect of thepresent invention, there is provided a floor polish compositioncomprising an aqueous resin dispersion for floors in which a copolymercomprising the monomer units (a), (b), and (c) as the structural unitsis dispersed in water, wherein the content ratios of each monomer in theaqueous resin dispersion for floors, based on the total amount of allthe monomers, are:

-   -   1 to 70 wt. % vinyl monomer units with an alicyclic structure;    -   5 to 50 wt. % vinyl monomer units with carboxyl groups; and    -   5 to 90 wt. % non-aromatic vinyl monomer units other than (a)        and (b) above, and    -   the copolymer is not metal crosslinked. In accordance with the        fourth aspect of the present invention, there is provided a        floor polish composition wherein the above-described aqueous        resin dispersion for floors comprises at least one compound        selected from cyclohexyl methacrylate and cyclohexyl acrylate as        the monomer component (a). In accordance with the fifth aspect        of the present invention, there is provided the floor polish        composition, wherein the glass transition temperature (Tg) of        the aqueous resin dispersion for floors is 40-115° C. and the        acid value (Av) thereof is 60-150. In particular, in accordance        with the sixth aspect of the present invention, there is        provided the floor polish composition which is used for        flooring.

The aqueous resin dispersion for floors in accordance with the presentinvention and the floor polish composition using same are preferablyused on plastic floors such as vinyl-based or synthetic resin-coatedfloors, stone floors, cement floors, flooring (wood floors), and thelike. The floor polish composition in accordance with the presentinvention has excellent gloss, black heel mark (BHM) resistance, scuffresistance, and storage stability, can be readily stripped within ashort time by using neutral stripping detergents, without using alkalinestripping detergent compositions, and when coated on flooring, hasexcellent stain resistance, for example, to condiments and detergentsused in kitchens and the like, thereby preventing the floor from damage.In particular, though the aqueous resin dispersion for floors containssubstantially no aromatic vinyl monomers, the floor polish compositionin accordance with the present invention has good removability, stainresistance, and water resistance. Further, the dispersion has no effectssuch as sick house syndrome, and because no metal crosslinking is used,the dispersion has excellent environmental safety.

The preferred embodiment of the present invention will be describedhereinbelow in detail.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The aqueous resin dispersion for floors in accordance with the presentinvention is composed of (a) vinyl monomer units with an alicyclicstructure, (b) vinyl monomer units with carboxyl groups, and (c)non-aromatic vinyl monomer units other than (a) and (b) above andcontains substantially no aromatic vinyl monomers.

Examples of vinyl monomer units having alicyclic structure, which arethe component (a) of the aqueous resin dispersion for floors inaccordance with the present invention, include cyclohexyl methacrylate,cyclohexyl acrylate, isobornyl methacrylate, isobornyl acrylate, and thelike. Among them, at least one compound selected from cyclohexylmethacrylate and cyclohexyl acrylate is preferably elected because sucha selection allows the coating film with excellent gloss and enduranceto be formed on the substrate surface and also allows the strippingoperation to be conducted easily with a neutral stripping agent when thecoating film has to be removed.

The vinyl monomer with an alicyclic structure, which is the component(a), is composed of one or more types of the above-described monomerunits and is mixed and copolymerized with other monomers at a ratio of1-70 wt. %, preferably 5-60 wt. %, in the aqueous resin dispersion forfloors. If the ratio of component (a) is less than 1 wt. %, the adhesiveproperties are degraded, and if it is above 70 wt. %, polymerizationsometimes becomes difficult.

Further, examples of the vinyl monomer with a carboxyl group, which isthe component (b) of the aqueous resin dispersion for floors inaccordance with the present invention, include acrylic acid, methacrylicacid, crotonic acid, itaconic acid, fumaric acid, maleic acid,monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, itaconicacid, citraconic acid, maleic anhydride, and the like. Among them,acrylic acid and methacrylic acid are preferred because of low costthereof and good copolymerization ability with other monomers.

The vinyl monomer with a carboxyl group, which is the component (b), iscomposed of one or more types of the above-described monomer units andis mixed and copolymerized with other monomers at a ratio of 5-50 wt. %,preferably, 9-25 wt. %, in the aqueous resin dispersion for floors. Ifthe ratio of component (b) is less than 5 wt. %, endurance andremovability are degraded, and if it is above 50 wt. %, the coating filmhas poor resistance to water and stain resistance.

Examples of the nonaromatic vinyl monomer, other that theabove-described (a) and (b) monomers, which is the component (c) of theaqueous resin dispersion for floors in accordance with the presentinvention, include (meth)acrylic acid esters such as methylmethacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate,isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate,n-butyl acrylate, isobutyl methacrylate, isobutyl acrylate, octylmethacrylate, octyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexylacrylate, lauryl methacrylate, lauryl acrylate, hydroxyethylmethacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate,hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutylacrylate, hydroxypolyoxyethylene methacrylate, hydroxypolyoxyethyleneacrylate, hydroxypolyoxypropylene methacrylate, hydroxypolyoxypropyleneacrylate, hydroxypolyoxybutylene methacrylate, hydroxypolyoxybutyleneacrylate, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allylacrylate, and the like, vinyl monomers other than (meth)acrylic acidesters, dienes such as butadiene, chloroprene, isoprene, and the like,vinyl esters such as vinyl acetate and the like, vinyl chloride,vinylidene chloride, methacrylonitrile, acrylonitrile, N-vinylpyrrolidone, and the like. From the standpoint of endurance and weatherresistance the preferred among them are methyl methacrylate, methylacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate,ethyl acrylate, ethyl methacrylate, isobutyl acrylate, and isobutylmethacrylate.

The aromatic vinyl monomer, other than the above-described components(a) and (b), which is the component (c), is composed one or more typesof the above-described monomer units and is mixed and copolymerized withother monomers at a ratio of 5-90 wt. %, preferably, 30-85 wt. %, in theaqueous resin dispersion for floors. If the ratio of component (c) isabove 90 wt. %, the balance of water resistance and endurance is poor.

On the other hand, styrene, □-methylstyrene, 4-methylstyrene,2-methylstyrene, 3-methylstyrene, 4-methoxystyrene,2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene,3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene,4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene,2,6-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, benzylmethacrylate, benzyl acrylate, which are aromatic vinyl monomers, aresubstantially not contained as the structural units of the copolymer ofthe aqueous resin dispersion for floors in accordance with the presentinvention.

The aqueous resin dispersion for floors in accordance with the presentinvention is preferably prepared by employing a well-known emulsionpolymerization method using the below described emulsifiers andpolymerization initiators.

Examples of suitable emulsifiers include anionic surfactants such assodium alkylbenzene sulfonates, sodium alkyl sulfates, sodiumpolyoxyethylene alkylphenyl ether sulfates, sodium polyethylene alkylsulfates, sodium dialkyl sulfosuccinates, formalin condensate ofnaphthalenesulfonic acid, and the like, nonionic surfactants, such aspolyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers,polyethylene glycol fatty acid esters, sorbitan fatty acid esters, andthe like, reactive emulsifiers such as sodium styrene sulfonate, sodiumalkylallyl sulfonates, sodium alkylallyl sulfosuccinates,polyoxyethylene alkylallyl glycerin ether sulfate, polyoxyethylenealkylphenol alkyl glycerin ether sulfate, and the like, polymersurfactants such as polyvinyl alcohol, polyacrylic acid, water-soluble(meth)acrylic acid ester copolymers, styrene-maleic acid copolymer andsalts thereof, styrene-(meth)acrylic acid copolymer and salts thereof,poly(meth)acrylamide copolymer, and the like. Those components may beused individually or in combinations of two or more thereof. Thepreferred quantity of the emulsifier used is usually 0.05-5 parts byweight per 100 parts by weight of the monomers. If the quantity of theemulsifier used is less than 0.05 part by weight, the emulsifier has apoor emulsifying ability. On the other hand, if the quantity if above 5parts by weight, water resistance can be insufficient.

Examples of suitable polymerization initiators include peroxodisulfatessuch as potassium peroxodisulfate, ammonium peroxodisulfate, sodiumperoxodisulfate, and the like, and peroxides such as hydrogen peroxide,benzoyl peroxide, t-butyl hydroxyperoxide, and the like. Thoseinitiators may be used as a redox system also using a reducing agentsuch as sodium bisulfite, sodium pyrobisulfite, ascorbic acid, sodiumformaldehyde sulfoxylate, and the like.

The polymerization reaction temperature is preferably 20-95° C., morepreferably, 40-90° C. The polymerization time is preferably 1-10 hours.

In the aqueous resin dispersion for floors in accordance with thepresent invention, the glass transition temperature of the copolymer ispreferably 10-115° C., more preferably, 40-155° C. When the glasstransition temperature of the copolymer is below 10° C., blocking easilyoccurs in the coating film, and when the glass transition temperatureexceeds 115° C., film forming ability at normal temperature is degraded.

Therefore, when the aqueous resin dispersion for floors is designed itis preferred that one or more types of each of the above-describedmonomer units (a), monomer units (b), and monomer units (c) be selectedsuch as to set the glass transition temperature (Tg) of the obtainedcopolymer within the above-described range. The glass transitiontemperature (called Tg hereinbelow) as referred to in the description ofthe present invention can be found from the Fox formula 1 shown below.1/Tg=W1/Tg1+W2/Tg2+W3/Tg3 . . .where W1, W2, W3, . . . are weight ratios of monomer units 1, 2, 3 inthe polymer, and Tg1, Tg2, Tg3 . . . are glass transition temperatures(in the above formula, absolute temperatures are used) of thehomopolymers of those monomer units 1, 2, 3 . . . .

In the above formula, values presented in polymer handbooks can be usedfor the glass transition temperature (Tg) of homopolymers. For example,poly(methyl methacrylate): 105° C., poly(n-butyl acrylate): −54° C.,poly(2-ethylhexyl acrylate): −50° C., poly(cyclohexyl acrylate): 19° C.,polymethacrylic acid: 228° C., poly(cyclohexyl methacrylate): 66° C.,polyacrylic acid: 106° C., polystyrene: 100° C., and the like.

The aqueous resin dispersion for floors in accordance with the presentinvention can be used as an aqueous dispersion with a concentration ofsolids of 10-70 wt. % and can be added to the floor polish compositionfor floors in accordance with the present invention within a range of10-60 wt. % as solids.

The floor polish composition for floors in accordance with the presentinvention is composed by using components such as a plasticizer, a filmformation enhancing agent, an alkali solubilizable resin, aslip-regulating agent, a wettability-improving agent, which are thewell-known components, in addition to the above-described aqueous resindispersion for floors.

Examples of suitable plasticizers include citric acid esters such asacetyltributyl citrate and the like, phosphoric acid esters such astributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate,tricresyl phosphate, tributoxyethyl phosphate, and the like, aliphaticdibasic acid esters such as dibutyl adipate, di-2-ethylhexyl adipate,di-n-alkyl (C6-10) adipate, di-2-ethylhexyl azelaate, dibutyl sebacate,di-2-ethylhexyl sebacate, and the like, isobutyl ester derivatives ofpentadiol, chlorinated paraffin, and the like.

Examples of film formation enhancing agents include alcohols such asethanol, isopropyl alcohol, and the like polyhydric alcohols such asethylene glycol and the like, glycol ethers such as diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, dipropylene glycolmonomethyl ether, dipropylene glycol monoethyl ether, ethylene glycolmono-2-methylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, andthe like, and amine compounds such as □-amino alcohol, □-amino alcoholdiethanolamine, triethanolamine, 2-aminoisohexyl alcohol,N,N-diethylethanolamine, N,N-dimethylethanolamine,aminoethylethanolamine, N-methyl-N,N-diethanolamine,N,N-butylethanolamine, N-methylethanolamine, 3-amino-1-propanol, and thelike.

However, in order to provide for a higher environmental safety, it ispreferred that the amine compounds be compounded in a small amount or besubstantially not compounded.

Examples of suitable alkali solubilizable resins includediisobutylene-maleic anhydride copolymer, rosin-modified maleic acid,(meth)acrylic acid ester-(meth)acrylic acid copolymer, shellac, and thelike. Those can be optionally used in the floor polish composition inaccordance with the present invention.

Examples of slip-regulating agents include vegetable waxes such ascandelilla wax, carnauba wax, rice wax, Japan wax, jojoba oil, and thelike, animal waxes such as beeswax, lanolin, whale tallow, and the like,mineral waxes such as montana wax, ozokerite, ceresin, and the like,petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum,and the like, synthetic hydrocarbon waxes such as Fischer-Tropsch wax,and the like, and synthetic waxes such as (oxidized) polyethylene wax,(oxidized) polypropylene wax, and the like.

Examples of suitable wettability-improving agents includefluorine-containing surfactants, silicone-type surfactants, anionicsurfactants such as higher alcohol sulfuric acid ester sodium, sodiumalkylbenzene sulfonate, sodium succinic acid dialkyl ester sulfonate,sodium, alkyldiphenyl ether sulfonate, polyoxyethylene alkyl sulfuricacid ester sodium, polyoxyethylene alkylphenyl ether sulfuric acid estersodium, sodium alkanesulfonates, and the like, polyoxyethylene alkylethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylenepolyoxypropylene copolymers, fatty acid esters such as sucrose fattyacid esters, sorbitan fatty acid esters, polyethylene glycol fatty acidesters, polyglycerin fatty acid esters, and the like, fatty acidalkanolamides such as coconut oil fatty acid diethanolamide, lauric aciddiethanolamide, lauric acid myristic acid diethanolamide, myristic aciddiethanolamide, oleic acid diethanolamide, palm kernel oildiethanolamide, and the like, nonionic surfactants such asalkylglycosides and the like, and amphoteric surfactants such asalkylbetaine amphoteric surfactants such as laurylbetaine and the like,amidobetaine amphoteric surfactants such as lauroylamidopropylbetaineand the like, imidazoline amphoteric surfactants such as2-alkyl-N-carboxymethyl imidazolinium betaine, 2-alkyl-N-carboxyethylimidazolinium betaine, and the like, alkylsulfobetaine amphotericsurfactants, amidosulfobetaine amphoteric surfactants such as coconutfatty acid amidodimethyl hydroxypropyl sulfobetaine, and the like, and□-alanine amphoteric surfactants such as N-alkyl-□-aminopropionate,N-alkyl-□-iminodipropioniate, and the like.

In addition, pH-adjusting agents such as ammonia and the like, corrosioninhibitors, antifoaming agents, bactericidal agents, perfumes,colorants, urethane resins, colloidal silica, fluorescent whiteners, UVabsorbers, and the like can be also used as optional components.

Further, it is also preferred that the floor polish composition inaccordance with the present invention contain substantially nopolyvalent metal compounds (heavy metals and the like) for metalcrosslinking, such as zinc oxide, calcium oxide, calcium hydroxide,aluminum hydroxide, zinc carbonate ammonia, calcium carbonate ethylenediamine-ammonia, zinc acetate ammonia, zinc acrylate ammonia, zincmalate ammonia, alanine calcium ammonia, and the like. The polyvalentmetals as referred to herein are metals with a valence of no less thantwo. Specific examples of such metals include beryllium, magnesium,calcium, strontium, iron, cobalt, nickel, zinc, manganese, copper,cadmium, lead, bismuth, barium, antimony, zirconium, and the like.Compounds of polyvalent metals are compounds containing those polyvalentmetals.

Those polyvalent metal compounds have been contained in the conventionalfloor polish compositions and have been used to provide the performancesuch as improved endurance, water resistance, and removability by amechanism of metal crosslinking of a metal and an acid component (e.g.,methacrylic acid and acrylic acid) contained in the polymer (polymers ofethylenic unsaturated compounds) in the drying process after coating aspolishing agents for floors. From the standpoint of environmental safetyassociated with increased concerns about environmental pollution, it ispreferred that substantially no polyvalent metal compounds (heavy metalsand the like) be contained.

The content ratio of nonvolatiles, including the above-describedoptional components, in the floor polish composition in accordance withthe present invention is preferably set at about 12-40 wt. %.

The preferred method for the manufacture of the floor polish compositioncomprises the steps of adding a plasticizer, a film formation enhancingagent, an alkali solubilizable resin, and a fluorine-containingsurfactant to water, then adding the aqueous resin dispersion for floorsin accordance with the present invention, and mixing a synthetic wax orthe like. Further, if necessary, optional components such aspH-adjusting agents such as ammonia and the like, corrosion inhibitors,antifoaming agents, bactericidal agents, perfumes, colorants, urethaneresins, colloidal silica, fluorescent whiteners, UV absorbers, and thelike, can be added at an appropriate stage of the process.

The floor polish composition in accordance with the present invention iseffective for application to a substrate, e.g., plastic floors such asvinyl floors, floors coated with synthetic resin, and the like, stonefloors, cement floors, wood flooring, and the like. The floor polishcomposition in accordance with the present invention can be applied tothe surface by the usual method such as spray coating, roller coating,brush coating, brushing, mopping, and the like. The floor polishcomposition can be used upon diluting with water or a solvent such as awater-miscible solvent, according to the apparatus specifications andcoating conditions. The adjustment of other coating conditions such astemperature, humidity, and the like can be conducted with an appropriatedrier, blower, air conditioner, and the like.

A removable protective film can be formed by drying the above-describedsubstrate coated with the floor polish composition in accordance withthe present invention, at normal temperature (5-35° C.±5° C.),preferably, at about 20-25° C. Means for water removal such as airblowing, heating, or both may be used appropriately in order to enhancethe evaporation of water in the protective film formation process. As aresult, the adjustment of protective film formation time is facilitated.However, heating means serves only for evaporating water, and heating isnot a necessary condition for forming the protective film.

EXAMPLES

Specific features of the aqueous resin dispersion for floors inaccordance with the present invention and the floor polish compositionusing such will be described based on the examples of the presentinvention and comparative examples. In the following description, theterm “parts” stands for parts by weight and “%”—percent by weight. Thepresent invention is not limited to those examples.

Aqueous Resin Dispersion for Floors

Preparation of Aqueous Resin Dispersion for Floors

A total of 60 parts of water and 0.5 part of sodium lauryl sulfate wereplaced in a reaction vessels equipped with a stirrer, a reflux cooler,two funnels, a thermometer, and a nitrogen inlet tube and thetemperature was raised to 85° C.

A total of 0.5 part of sodium lauryl sulfate and 35 parts of water wereadded to a mixture of monomers shown in Tables 1 through 4 andemulsification was conducted. The obtained monomer emulsions and 10parts of 5% aqueous solution of ammonium persulfate were continuouslydropwise added to a reaction vessel within 3 hours via separate droppingfunnels and emulsion polymerization was conducted. Within 1 hour aftercompletion of the dropwise addition, the system was cooled,polymerization was completed and an aqueous resin dispersion for floorswas obtained.

Further, the monomer composition of each polymer, the number of weightparts, glass transition temperature (° C.), acid value, and amount ofnonvolatile components (%) are shown together.

In Tables 1 through 4, CHA stands for cyclohexyl acrylate,CHMA—cyclohexyl methacrylate, nBA—n-butyl acrylate, 2EHA—2-ethylhexylacrylate, AA—acrylic acid, MAA—methacrylic acid, MMA—methylmethacrylate, ST—styrene, Tg—glass transition temperature, AV—acidvalue, amount of nonvolatile compounds—effective amount of polymers inthe aqueous resin dispersion for floors. TABLE 1 Aqueous resindispersion for floors 1 2 3 4 5 a CHA 31.0 31.0 31.0 10.0 CHMA 45.0 bMAA 10.0 15.0 15.0 19.3 15.0 AA c nBA 11.0 18.0 12.5 14.2 26.0 2EHA MMA48.0 22.0 41.5 35.5 49.0 ST TOTAL 100.0 100.0 100.0 100.0 100.0 Tg (°C.) 57 57 57 57 47 ACID VALUE 65 98 98 126 98 AMOUNT OF 40.0 40.0 40.040.0 40.0 NON-VOLATILE COMPONENTS (%)

TABLE 2 Aqueous resin dispersion for floors 6 7 8 9 10 a CHA 26.0 31.031.0 50.0 CHMA 5.0 31.0 b MAA 5.0 15.0 15.0 15.0 AA 5.0 7.7 c nBA 10.09.0 7.5 5.0 2EHA 19.0 MMA 49.0 35.0 45.0 53.8 30.0 ST TOTAL 100.0 100.0100.0 100.0 100.0 Tg (° C.) 58 61 65 57 57 ACID VALUE 72 98 98 60 98AMOUNT OF 40.0 40.0 40.0 40.0 40.0 NON-VOLATILE COMPONENTS (%)

TABLE 3 Aqueous resin dispersion for floors 11 12 13 14 15 a CHA 30.030.0 5.0 1.0 31.0 CHMA b MAA 20.5 22.0 15.0 16.0 19.3 AA c nBA 10.0 10.014.2 2EHA MMA 39.5 38.0 80.0 83.0 18.0 ST 17.5 TOTAL 100.0 100.0 100.0100.0 100.0 Tg (° ^(C.)) 67 68 114 119 56 ACID VALUE 134 143 98 104 126AMOUNT OF 40.0 40.0 40.0 40.0 40.0 NON-VOLATILE COMPONENTS (%)

TABLE 4 Aqueous resin dispersion for floors 16 17 18 19 20 a CHA CHMA15.0 b MAA 19.3 8.5 24.0 16.0 15.0 AA c nBA 28.0 24.8 25.0 23.0 30.02EHA MMA 13.0 66.7 31.0 55.0 ST 39.7 20.0 46.0 TOTAL 100.0 100.0 100.0100.0 100.0 Tg (° C.) 53 53 63 55 47 ACID VALUE 126 55 126 104 98 AMOUNTOF 40.0 40.0 40.0 40.0 40.0 NON-VOLATILE COMPONENTS (%)

Floor polish compositions of Example 1 through 18 and ComparativeExamples 1 through 10 shown in Tables 5 through 9 were prepared by usingpolymers of the aqueous resin dispersion for floors shown in Tables 1through 4, and each of the compositions was tested. The numerical valuesin the tables represent the content in wt. %, and the effective contentof each component is presented in the footnotes.

Gloss, black heel mark (BHM) resistance, scuff resistance, storagestability, stain resistance, water resistance, removability, waterresistance, and environmental safety of the floor polish compositionsobtained were evaluated by the following test methods and evaluationcriteria. The results are shown in Tables 10 through 14.

Gloss

[Test Method]

In accordance with JIS K 3920 (Test Methods for Floor Polishes), samplesof the floor polish compositions were coated three times on homogeneousvinyl tiles (manufactured by Tori K.K., Machiko S Plain No. 5626). Thegloss of the coating dried for 1 hour was measured with a mirror surfacegloss meter (manufactured by Nippon Denshoku Kogyo K.K., model PG-1M).

(2) Black Heel Mark (BHM) Resistance

In accordance with JIS K 3920 (Test Methods for Floor Polishes), samplesof the floor polish compositions were coated three times on homogeneousvinyl tiles (manufactured by Tori K.K., Machiko S Plain No. 5626). Thecoatings dried overnight at normal temperature were tested with a heelmark tester and evaluated visually according to 10 grades.

[Evaluation Criteria]

-   -   10: A very high BHM resistance is demonstrated.    -   6-9: An appropriate BHM resistance is demonstrated, the polish        is suitable for practical use.    -   2-5: Poor BHM resistance, the polish is not suitable for        practical use.    -   1: Very poor BHM resistance.

(3) Scuff Resistance

In accordance with JIS K 3920 (Test Methods for Floor Polishes), thesamples of the floor polish compositions were coated three times onhomogeneous vinyl tiles (manufactured by Tori K.K., Machiko S Plain No.5626). The coatings dried overnight at normal temperature were testedwith a heel mark tester and evaluated visually according to 10 grades.

[Evaluation Criteria]

-   -   10: A very high scuff resistance is demonstrated.    -   6-9: An appropriate scuff resistance is demonstrated, the polish        is suitable for practical use.    -   2-5: Poor scuff resistance, the polish is not suitable for        practical use.    -   1: Very poor scuff resistance.

(4) Storage Stability

In accordance with JIS K 3920 (Test Methods for Floor Polishes), thefloor polish compositions were placed into containers, sealed therein,and held for 14 days in a thermostat (manufactured by Isuzu SeisakushoK.K., model KAX-730) maintained at 50° C. The state of the samples wasthen visually evaluated according to the following criteria with respectto gelling, phase separation, precipitation of solids, and the like.

[Evaluation Criteria]

-   -   Conforms: No problems are observed.    -   Does not conform: Problems are observed.

(5) Stain Resistance

The samples of the floor polish compositions were coated twice onflooring (manufactured by Asahi Woodtech Co., Ltd., SHG-6020MII) anddried overnight at normal temperature. Then, the detergents andcondiments described below (diluted or as original liquids: a-j) werelet fall in 0.1 mL drops on the floor and covered with a laboratory dishto prevent them from evaporating. Within 1 hour, the laboratory dish wasremoved, the liquid was soaked up with soft fabric, paper, or the like,and the state of the flooring tile surface was evaluated visuallyaccording to the following evaluation criteria.

-   -   Whitener for kitchens

(Commercial chlorine whitener comprising sodium hypochlorite and asodium alkyl ether sulfate. The test is conducted by using an aqueouswhitener solution prepared by dissolving 1 mL of the whitener in 1 L ofwater).

-   -   Synthetic detergent for kitchen

(Commercial neutral detergent for kitchens comprising a sodium alkylether sulfate, an alkylamineoxide, a fatty acid alkanolamide, and asodium □-olefin sulfonate).

-   -   Synthetic detergent for washing

(Commercial powdered washing detergent comprising a straight-chainsodium alkylbenzene sulfonate, a polyoxyethylene alkyl ether, analuminosilicate, a carbonate, a silicate, and a phosphate). The test isconducted by using an aqueous detergent solution prepared by dissolving1 g of the detergent in 1 L of water).

-   -   Vinegar    -   Mayonnaise    -   Soy sauce    -   Salad oil    -   Japanese sake    -   Hair dye    -   Hair conditioner

[Evaluation Criteria]

-   -   Good: No whitening and peeling are observed.    -   Fair: Some whitening and peeling are observed.    -   Poor: Whitening and peeling.

(6) Removability

[Test Method]

In accordance with JIS K 3920 (Test Methods for Floor Polishes), thesamples of the floor polish compositions were coated three times oncomposition tiles (manufactured by Tori K.K., New-Machiko No. 33) anddried for 7 days at a temperature of 50° C. The test was then conductedwith a washability tester (Tester Sangyo Co., Ltd., model AB-504) byusing a neutral stripping agent (Johnson Professional Co., Ltd., tradename Neutra Stripper). The results were evaluated visually according tothe following evaluation criteria.

The test results obtained by using a 5-fold aqueous solution of NeutraStripper are shown as removability (1) and the test results obtained byusing a 10-fold aqueous solution of Neutra Stripper are shown asremovability (2).

[Evaluation Criteria]

-   -   Very good: Can be removed completely.    -   Good: Can be removed almost completely.    -   Fair: Some film remains.    -   Poor: Practically cannot be removed.

(7) Water Resistance

[Test Method]

In accordance with JIS K 3920 (Test Methods for Floor Polishes), thesamples of the floor polish compositions were coated three times oncomposition vinyl tiles (manufactured by Tori K.K., New-Machiko V No.33) and dried overnight under an atmosphere at a temperature of 38° C.Then, water was let fall in 0.1 mL drops. Within 1 hour, the whiteningstate of the composition vinyl tile surface was visually evaluated.

[Evaluation Criteria]

-   -   Conforms: No whitening is observed.    -   Does not conform: Whitening is observed.

(8) Adhesive Properties

[Test Method]

A cellotape (trade name) adhesion test was conducted on the surface ofspecimens prepared by coating the samples of the floor polishcompositions four times on homogeneous vinyl tiles (manufactured by ToriK.K., Machiko S Plain No. 5626) and drying for 1 hour at roomtemperature. The surface area (%) of remaining film averaged for fivemeasurement cycles is shown. In the evaluation, adhesion to the floorsurface subjected to conventional washing was reproduced.

(9) Environmental Safety

[Test Method]

The evaluation was conducted based on the following evaluation criteriawith respect to the presence of styrene and polyvalent metal compounds(heavy metals and the like) in the floor polish composition samples.

[Evaluation Criteria]

-   -   Good: Contains substantially none.

Poor: Contains. TABLE 5 EXAMPLES 1 2 3 4 5 6 AQUEOUS 1 35.00 33.00 30.0033.00 RESIN 2 35.00 32.00 DISPERSION 3 2.00 FOR FLOORS 4 5.00 5 2.00 63.00 7 8 9 10 11 12 13 14 15 16 17 18 19 20 *1 *2 1.00 1.00 1.00 1.001.00 1.00 *3 0.01 0.01 0.01 0.01 0.01 0.01 *4 7.00 7.00 7.00 7.00 7.007.00 *5 3.00 3.00 3.00 3.00 3.00 3.00 *6 1.50 1.50 1.50 1.50 1.50 1.50*7 6.00 6.00 6.00 6.00 6.00 6.00 *8 *9 DIETHANOLAMINE DEIONIZED WATERBALANCE BALANCE BALANCE BALANCE BALANCE BALANCE TOTAL 100.00 100.00100.00 100.00 100.00 100.00

The components shown in the table are described below. This descriptionalso relates to Tables 6 through 9.

*1: Aqueous polyurethane resin (acid value about 98) composed of 4.9parts of polypropylene glycol (molecular weight 1,000), 7.0 parts ofdimethylolpropionic acid, 17.6 parts of dicylohexylmethane diisocyanate,0.5 part hexamethylenediamine, 4.8 parts of triethylamine, 19.6 parts ofN-methylpyrrolidone, and 45.6 parts of distilled water.

*2: Fluorine-containing surfactant: S-100 (manufacture by Ciba SpecialtyChemicals Co., Ltd., fluorine-containing surfactant: 1% aqueoussolution).

*3: Antifoaming agent: SE-21 (manufactured by WSC Co., Ltd., antifoamingagent, fineness 17%).

*4: Wax emulsion: High-Tech E-4000 (Toho Chemical Industry Co., Ltd.,polyethylene wax emulsion, fineness 40%).

*5: Alkali solubilizable resin: TOPCO LR400 (Toyo Petrolite Co., Ltd.,rosin maleic acid solution, fineness 30%).

*6: Plasticizer: tributoxyethyl phosphate (manufactured by DaihachiChemical Industry Co., Ltd., a plasticizer).

*7: Film formation enhancing agent: diethylene glycol monoethyl ether.

*8: Crosslinking agent 1: aqueous solution of ammonium complex of zinccarbonate (content of zinc is 9.6%).

*9: Crosslinking agent 2: calcium carbonate. TABLE 6 EXAMPLES 7 8 9 1011 12 AQUEOUS 1 RESIN 2 30.00 30.00 33.00 33.00 32.00 32.00 DISPERSION 3FOR FLOORS 4 5 6 7 5.00 8 5.00 9 2.00 10 2.00 11 3.00 12 3.00 13 14 1516 17 18 19 20 *1 *2 1.00 1.00 1.00 1.00 1.00 1.00 *3 0.01 0.01 0.010.01 0.01 0.01 *4 7.00 7.00 7.00 7.00 7.00 7.00 *5 3.00 3.00 3.00 3.003.00 3.00 *6 1.50 1.50 1.50 1.50 1.50 1.50 *7 6.00 6.00 6.00 6.00 6.006.00 *8 *9 DIETHANOLAMINE DEIONIZED WATER BALANCE BALANCE BALANCEBALANCE BALANCE BALANCE TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 7 EXAMPLES 13 14 15 16 17 18 AQUEOUS 1 35.00 30.00 RESIN 2 32.0032.00 35.00 32.00 DISPERSION 3 FOR FLOORS 4 5.00 5 6 3.00 7 8 9 10 11 1213 3.00 14 3.00 15 16 17 18 19 20 *1 *2 1.00 1.00 1.00 1.00 1.00 1.00 *30.01 0.01 0.01 0.01 0.01 0.01 *4 7.00 7.00 7.00 7.00 7.00 7.00 *5 3.003.00 *6 1.50 1.50 1.50 1.50 1.50 1.50 *7 6.00 6.00 6.00 6.00 6.00 6.00*8 *9 DIETHANOLAMENE DEIONIZED WATER BALANCE BALANCE BALANCE BALANCEBALANCE BALANCE TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 8 COMPARATIVE EXAMPLES 1 2 3 4 5 6 AQUEOUS 1 RESIN 2 DISPERSION 3FOR FLOORS 4 5 6 7 8 9 10 11 12 13 14 15 35.00 16 35.00 17 35.00 1835.00 19 35.00 20 35.00 *1 *2 1.00 1.00 1.00 1.00 1.00 1.00 *3 0.01 0.010.01 0.01 0.01 0.01 *4 7.00 7.00 7.00 7.00 7.00 7.00 *5 3.00 3.00 3.003.00 3.00 3.00 *6 1.50 1.50 1.50 1.50 1.50 1.50 *7 6.00 6.00 6.00 6.006.00 6.00 *8 *9 DIETHANOLAMINE DEIONIZED WATER BALANCE BALANCE BALANCEBALANCE BALANCE BALANCE TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 9 COMPARATIVE EXAMPLES 7 8 9 10 AQUEOUS 1 RESIN 2 DISPERSION 3 FORFLOORS 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 28.00 19 37.30 37.30 2010.00 *1 33.33 *2 0.50 3.60 0.60 3.60 *3 0.02 0.01 0.02 *4 5.62 6.8210.00 6.82 *5 2.50 3.00 *6 1.20 1.14 1.33 1.14 *7 4.80 3.33 4.00 3.33 *83.00 3.00 *9 0.35 DIETHANOLAMINE 8.00 DEIONIZED WATER BALANCE BALANCEBALANCE BALANCE TOTAL 100.00 100.00 100.00 100.00

TABLE 10 EXAMPLE 1 2 3 4 5 6 GLOSS DEGREE 80 82 80 80 81 81 BHMRESISTANCE 6 6 6 6 6 6 SCUFF RESISTANCE 6 6.5 6 6.5 6 6 STORAGESTABILITY CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS STAIN aGOOD GOOD GOOD GOOD GOOD GOOD RESISTANCE b GOOD GOOD GOOD GOOD GOOD GOODc GOOD GOOD GOOD GOOD GOOD GOOD d GOOD GOOD GOOD GOOD GOOD GOOD e GOODGOOD GOOD GOOD GOOD GOOD f GOOD GOOD GOOD GOOD GOOD GOOD g GOOD GOODGOOD GOOD GOOD GOOD h GOOD GOOD GOOD GOOD GOOD GOOD i GOOD GOOD GOODGOOD GOOD GOOD j GOOD GOOD GOOD GOOD GOOD GOOD WATER RESISTANCE CONFORMSCONFORMS CONFORMS CONFORMS CONFORMS CONFORMS REMOVABILITY 1 VERY GOODVERY GOOD VERY GOOD VERY GOOD VERY GOOD VERY GOOD 2 GOOD GOOD GOOD GOODGOOD GOOD ADHESIVE PROPERTIES 100 100 100 100 100 100 ENVIRONMENTALSAFETY GOOD GOOD GOOD GOOD GOOD GOOD TOTAL EVALUATION GOOD GOOD GOODGOOD GOOD GOOD

TABLE 11 EXAMPLE 7 8 9 10 11 12 GLOSS DEGREE 79 81 82 81 80 80 BHMRESISTANCE 6 6 6 6 6 6 SCUFF RESISTANCE 6.5 6 6 5.5 5.5 5.5 STORAGESTABILITY CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS STAIN aGOOD GOOD GOOD GOOD GOOD GOOD RESISTANCE b GOOD GOOD GOOD GOOD GOOD GOODc GOOD GOOD GOOD GOOD GOOD GOOD d GOOD GOOD GOOD GOOD GOOD GOOD e GOODGOOD GOOD GOOD GOOD GOOD f GOOD GOOD GOOD GOOD GOOD GOOD g GOOD GOODGOOD GOOD GOOD GOOD h GOOD GOOD GOOD GOOD GOOD GOOD i GOOD GOOD GOODGOOD GOOD GOOD j GOOD GOOD GOOD GOOD GOOD GOOD WATER RESISTANCE CONFORMSCONFORMS CONFORMS CONFORMS CONFORMS CONFORMS REMOVABILITY 1 VERY GOODVERY GOOD VERY GOOD VERY GOOD VERY GOOD VERY GOOD 2 GOOD GOOD GOOD GOODGOOD GOOD ADHESIVE PROPERTIES 100 100 100 100 100 100 ENVIRONMENTALSAFETY GOOD GOOD GOOD GOOD GOOD GOOD TOTAL EVALUATION GOOD GOOD GOODGOOD GOOD GOOD

TABLE 12 EXAMPLE 13 14 15 16 17 18 GLOSS DEGREE 79 76 80 83 81 81 BHMRESISTANCE 6 6 6 6 6 6 SCUFF RESISTANCE 5.5 6 6 6.5 6.5 6 STORAGESTABILITY CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS STAIN aGOOD GOOD GOOD GOOD GOOD GOOD RESISTANCE b GOOD GOOD GOOD GOOD GOOD GOODc GOOD GOOD GOOD GOOD GOOD GOOD d GOOD GOOD GOOD GOOD GOOD GOOD e GOODGOOD GOOD GOOD GOOD GOOD f GOOD GOOD GOOD GOOD GOOD GOOD g GOOD GOODGOOD GOOD GOOD GOOD h GOOD GOOD GOOD GOOD GOOD GOOD i GOOD GOOD GOODGOOD GOOD GOOD j GOOD GOOD GOOD GOOD GOOD GOOD WATER RESISTANCE CONFORMSCONFORMS CONFORMS CONFORMS CONFORMS CONFORMS REMOVABILITY 1 VERY GOODVERY GOOD VERY GOOD VERY GOOD VERY GOOD VERY GOOD 2 GOOD GOOD GOOD GOODGOOD GOOD ADHESIVE PROPERTIES 100 95 100 100 100 100 ENVIRONMENTALSAFETY GOOD GOOD GOOD GOOD GOOD GOOD TOTAL EVALUATION GOOD GOOD GOODGOOD GOOD GOOD

TABLE 13 COMPARATIVE EXAMPLE 1 2 3 4 5 6 GLOSS DEGREE 83 86 70 77 88 71BHM RESISTANCE 6 6 5 6 7 6 SCUFF RESISTANCE 6 5.5 5 6 7 6 STORAGESTABILITY CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS CONFORMS STAIN aGOOD POOR POOR POOR POOR POOR RESISTANCE b GOOD GOOD GOOD POOR GOOD POORc POOR POOR POOR POOR POOR POOR d GOOD GOOD GOOD GOOD GOOD GOOD e GOODGOOD GOOD GOOD GOOD GOOD f GOOD GOOD GOOD GOOD GOOD GOOD g GOOD GOODGOOD GOOD GOOD GOOD h GOOD GOOD GOOD GOOD GOOD GOOD i GOOD GOOD GOODGOOD GOOD GOOD j GOOD GOOD GOOD GOOD GOOD GOOD WATER RESISTANCE CONFORMSCONFORMS CONFORMS CONFORMS CONFORMS CONFORMS REMOVABILITY 1 GOOD FAIRFAIR GOOD FAIR GOOD 2 FAIR POOR POOR FAIR POOR FAIR ADHESIVE PROPERTIES100 50 40 70 100 50 ENVIRONMENTAL SAFETY POOR POOR GOOD POOR POOR GOODTOTAL EVALUATION POOR POOR POOR POOR POOR POOR

TABLE 14 COMPARATIVE EXAMPLE 7 8 9 10 GLOSS DEGREE 75  88 72  88 BHMRESISTANCE  6  7  6  7 SCUFF RESISTANCE  6  7  6  7 STORAGE STABILITYDOES NOT CONFORMS CONFORMS CONFORMS CONFORM STAIN a POOR POOR POOR POORRESISTANCE b GOOD GOOD POOR GOOD c POOR POOR POOR POOR d GOOD GOOD GOODGOOD e GOOD GOOD GOOD GOOD f GOOD GOOD GOOD GOOD g GOOD GOOD GOOD GOOD hGOOD GOOD GOOD GOOD i GOOD GOOD GOOD GOOD j GOOD GOOD GOOD GOOD WATERRESISTANCE CONFORMS CONFORMS CONFORMS CONFORMS REMOVABILITY 1 GOOD FAIRGOOD POOR 2 FAIR POOR FAIR POOR ADHESIVE PROPERTIES 70 100 50 100ENVIRONMENTAL SAFETY POOR POOR GOOD POOR TOTAL EVALUATION POOR POOR POORPOOR

The evaluation results obtained in Examples 1 to 18 make it apparentthat the floor polish composition in accordance with the presentinvention demonstrates good results for all the test items: gloss, blackheel mark (BHM) resistance, scuff resistance, storage stability, stainresistance, water resistance, removability, adhesive properties, andenvironmental safety. Furthermore, it is clear that the floor polishcomposition in accordance with the present invention demonstrates goodresults for all the test items even when it contains no alkalisolubilizable resin, as in Examples 15 to 18.

On the other hand, Comparative Examples 1 and 5 relate to the case inwhich the aqueous resin dispersions for floors comprise ST (styrene),while comprising a vinyl monomer with an alicyclic structure, which isthe monomer (a), and it is clear that those compositions have degradedremovability and environmental safety and also a slightly degraded stainresistance.

Further, Comparative Examples 2 and 4 relate to the case in which theaqueous resin dispersions for floors comprise ST (styrene), whilecomprising no vinyl monomer with an alicyclic structure, which is themonomer (a), and it is clear that those compositions have degraded stainresistance, removability, adhesive properties, and environmental safety.

The composition of Comparative Example 4 has removability and adhesiveproperties improved over those of the composition of Comparative Example2, but the stain resistance thereof is degraded and it is clear that thetotal evaluation of this composition cannot be considered satisfactory.

Further, Comparative Examples 3 and 6 relate to the case in which theaqueous resin dispersions for floors contain no vinyl monomer with analicyclic structure, which is the monomer (a), and no ST (styrene), andit is clear that those compositions have degraded gloss, stainresistance, removability, and adhesive properties.

The composition of Comparative Example 6 has removability and adhesiveproperties improved over those of the composition of Comparative Example3, but stain resistance thereof is degraded and it is clear that thetotal evaluation of this composition cannot be considered satisfactory.

Comparative Example 7 relates to the case in which the aqueous resindispersion for floors contains no vinyl monomer with an alicyclicstructure, which is the monomer (a), comprises ST (styrene) and iscrosslinked by amine compounds (equivalent to Examples 2 of JapanesePatent Application Laid-open No. 2001-2980). It is clear that thisdispersion has poor stain resistance, removability, adhesive properties,and environmental safety.

Comparative Example 8 relates to the case in which the aqueous resindispersion comprises a vinyl monomer with an alicyclic structure, whichis the monomer (a), and ST (styrene) and is crosslinked by zinc(equivalent to Example 2 of Japanese Patent Application Laid-open No.2000-290596). It is clear that this dispersion has poor removability andenvironmental safety and also slightly degraded stain resistance.

Comparative Example 9 relates to the case in which the aqueous resindispersion comprises a vinyl monomer with an alicyclic structure, whichis the monomer (a), and ST (styrene) and is crosslinked by calcium(equivalent to Example 3 of Japanese Patent Application Laid-open No.H8-92529). It is clear that this dispersion has poor stain resistance,removability and adhesive properties.

Comparative Example 10 relates to the case in which the alkalisolubilizable resin was removed from the conventional formulation shownin Comparative Example 8. It is clear that removability andenvironmental safety are degraded, in particular, removability isfurther degraded with respect to that of Comparative Example 8. In otherwords, an alkali solubilizable resin can be considered as a mandatoryingredient of the conventional floor polish compositions.

The present invention provides an aqueous resin dispersion composed ofspecific monomer units and a floor polish composition using same. Thecomposition can be advantageously used on substrates such as plasticfloors including vinyl floors and floors coated with synthetic resins,stone floors, cement floors, flooring (wood floors), and the like.

The present invention can provide a floor polish composition withexcellent gloss, black heel mark (BHM) resistance, scuff resistance, andstorage stability, in particular, having removability, adhesiveproperties, stain resistance, and water resistance. Because thecomposition uses no aromatic vinyl monomers for the aqueous resindispersion for floors, the composition has no effects such as sick housesyndrome, and because no metal crosslinking is used, the composition hasexcellent environmental safety.

Further, the floor polish composition in accordance with the presentinvention can be stripped easily and within a short time by usingneutral stripping detergents, without using alkaline stripping detergentcompositions, and when coated on flooring, has excellent stainresistance, for example, to condiments and detergents used in kitchensand the like, thereby preventing the floor from damage.

1. An aqueous resin dispersion for floors in which a copolymercomprising the monomer units (a), (b), and (c) as the structural unitsis dispersed in water, wherein the content ratios of each monomer insaid aqueous resin dispersion for floors, based on the total amount ofall the monomers, are: (a) 1 to 70 wt. % vinyl monomer units with analicyclic structure; (b) 5 to 50 wt. % vinyl monomer units with carboxylgroups; and (c) 5 to 90 wt. % non-aromatic vinyl monomer units otherthan (a) and (b) above.
 2. The aqueous resin dispersion for floorsaccording to claim 1, wherein the monomer unit (a) comprises at leastone compound selected from cyclohexyl methacrylate and cyclohexylacrylate.
 3. A floor polish composition comprising an aqueous resindispersion for floors in which a copolymer comprising the monomer units(a), (b), and (c) as the structural units is dispersed in water, whereinthe content ratios of each monomer in the aqueous resin dispersion forfloors, based on the total amount of all the monomers, are: (a) 1 to 70wt. % vinyl monomer units with an alicyclic structure; (b) 5 to 50 wt. %vinyl monomer units with carboxyl groups; and (c) 5 to 90 wt. %non-aromatic vinyl monomer units other than (a) and (b) above, and saidcopolymer is not metal crosslinked.
 4. The floor polish compositionaccording to claim 3, wherein said aqueous resin dispersion for floorscomprises at least one compound selected from cyclohexyl methacrylateand cyclohexyl acrylate as the monomer component (a).
 5. The floorpolish composition according to claim 3, wherein the glass transitiontemperature (Tg) of said aqueous resin dispersion for floors is in therange of 40 to 115° C. and the acid value (Av) thereof is in the rangeof 60 to
 150. 6. The floor polish composition according to claim 4,wherein the glass transition temperature (Tg) of said aqueous resindispersion for floors is in the range of 40 to 115° C. and the acidvalue (Av) thereof is in the range of 60 to
 150. 7. The floor polishcomposition according to claim 3, which is used for flooring.
 8. Thefloor polish composition according to claim 4, which is used forflooring.
 9. The floor polish composition according to claim 5, which isused for flooring.